Treatment to Control Deposition Rate

ABSTRACT

A treatment, structure and system are provided that modify the deposition process of a material that can occur over two differing materials. In an embodiment the deposition rates may be adjusted by the treatment to change the deposition rate of one of the materials to be more in line with the deposition rate of a second one of the materials. Also, the deposition rates may be modified to be different from each other, to allow for a more selective deposition over the first one of the materials than over the second one of the materials.

PRIORITY CLAIM AND CROSS-REFERENCE

This application is a division of U.S. patent application Ser. No.16/051,064, filed on Jul. 31, 2018, entitled “Treatment to ControlDeposition Rate,” which application is a division of U.S. patentapplication Ser. No. 14/942,407, filed on Nov. 16, 2015, entitled“Treatment to Control Deposition Rate,” now U.S. Pat. No. 10,388,515issued on Aug. 20, 2019, which applications are hereby incorporatedherein by reference in its entirety.

BACKGROUND

The semiconductor industry has experienced rapid growth due tocontinuous improvements in the integration density of a variety ofelectronic components such as transistors, diodes, resistors,capacitors, and the like onto a semiconductor substrate. For the mostpart, these improvements in integration density have come from repeatedreductions in minimum feature sizes, which allow more components to beintegrated into a given area of the semiconductor substrate.

However, as the demand for miniaturization, higher speeds, and greaterbandwidths, as well as lower power consumption and latency, has grown,there has also grown a need for smaller and smaller tolerances for thematerials and processes used to manufacture semiconductor devices. Inparticular, as the size of the transistors, diodes, resistors,capacitors, etc. have been reduced, the materials used to form thesedevices have also experienced a reduction in size. As such, techniquesto better reduce and better control these materials are constantly beingsought for further miniaturization.

BRIEF DESCRIPTION OF THE DRAWINGS

Aspects of the present disclosure are best understood from the followingdetailed description when read with the accompanying figures. It isnoted that, in accordance with the standard practice in the industry,various features are not drawn to scale. In fact, the dimensions of thevarious features may be arbitrarily increased or reduced for clarity ofdiscussion.

FIGS. 1A-1B illustrate a fin and a first masking layer in accordancewith some embodiments.

FIGS. 2-3 illustrate a treatment and deposition chamber in accordancewith some embodiments.

FIGS. 4A-4C illustrate a first treatment process in accordance with someembodiments.

FIGS. 5A-5D illustrate a deposition of a dielectric layer in accordancewith some embodiments.

FIGS. 6A-6C illustrate a formation of spacers in accordance with someembodiments.

FIGS. 7A-7C illustrate a second treatment in accordance with someembodiments.

FIGS. 8A-8C illustrate a deposition of the dielectric layer after thesecond treatment in accordance with some embodiments.

FIGS. 9A-9C illustrate a third treatment in accordance with someembodiments.

FIGS. 10A-10D illustrate a deposition of the dielectric layer after thethird treatment in accordance with some embodiments.

DETAILED DESCRIPTION

The following disclosure provides many different embodiments, orexamples, for implementing different features of the invention. Specificexamples of components and arrangements are described below to simplifythe present disclosure. These are, of course, merely examples and arenot intended to be limiting. For example, the formation of a firstfeature over or on a second feature in the description that follows mayinclude embodiments in which the first and second features are formed indirect contact, and may also include embodiments in which additionalfeatures may be formed between the first and second features, such thatthe first and second features may not be in direct contact. In addition,the present disclosure may repeat reference numerals and/or letters inthe various examples. This repetition is for the purpose of simplicityand clarity and does not in itself dictate a relationship between thevarious embodiments and/or configurations discussed.

Further, spatially relative terms, such as “beneath,” “below,” “lower,”“above,” “upper” and the like, may be used herein for ease ofdescription to describe one element or feature's relationship to anotherelement(s) or feature(s) as illustrated in the figures. The spatiallyrelative terms are intended to encompass different orientations of thedevice in use or operation in addition to the orientation depicted inthe figures. The apparatus may be otherwise oriented (rotated 90 degreesor at other orientations) and the spatially relative descriptors usedherein may likewise be interpreted accordingly.

With reference now to FIGS. 1A-1B, there is illustrated a substrate 101with a fin 103 (denoted as separate from the rest of the substrate 101by dashed line 102), a first masking layer 105 over the fin 103, and asecond masking layer 107. In an embodiment the substrate 101 maycomprise, for example, bulk silicon, doped or undoped, germanium, aIII-V material (such as gallium arsenide, indium arsenide, or the like),or an active layer of a semiconductor-on-insulator (SOI) substrate.Generally, an SOI substrate comprises a layer of a semiconductormaterial, such as silicon, formed on an insulator layer. The insulatorlayer may be, for example, a buried oxide (BOX) layer or a silicon oxidelayer. The insulator layer is provided on a substrate, typically asilicon or glass substrate. Other substrates, such as a multi-layered orgradient substrate may also be used.

The fin 103 may be formed from the substrate 101. In an embodiment thefin 103 may be formed from the substrate 101 by initially forming thepatterned mask 106 over the substrate 101. In an embodiment a patternedmask 106 may be a multi-layered structure that comprises the firstmasking layer 105 and the second masking layer 107 on top of the firstmasking layer 105. The first masking layer 105 may be a layer ofdielectric material such as silicon nitride, although any other suitablematerial, such as SiO₂ or SiON may be utilized. The first masking layer105 may be formed using a deposition process such as chemical vapordeposition (CVD), physical vapor deposition (PVD), or atomic layerdeposition (ALD) or else may be formed by nitridizing an upper portionof the fin 103. The first masking layer 105 may have a second thicknessT₂ of between about 5 nm and about 30 nm, such as about 10 nm.

Once the material for the first masking layer 105 has been formed overthe substrate 101, the second masking layer 107 is formed over the firstmasking layer 105. In an embodiment the second masking layer 107 is adielectric material such as silicon oxide, silicon oxynitride, or thelike. The second masking layer 107 may be formed using a depositionprocess such as CVD, PVD, ALD, or the like to a third thickness T₃ ofbetween about 10 nm and about 100 nm, such as about 40 nm. However, anysuitable deposition process, such as a deposition of silicon followed byan oxidation process, and any suitable thickness may be used.

The materials of the patterned mask 106 (e.g., silicon nitride for thefirst masking layer 105 and silicon oxide for the second masking layer107) are subsequently patterned using, for example, photolithographytechniques. Generally, photolithography techniques involve depositing aphotoresist material and irradiating the photoresist material inaccordance with a pattern. Thereafter, the photoresist material isdeveloped to remove a portion of the photoresist material. The remainingphotoresist material protects the underlying material during subsequentprocessing steps, such as etching. In this case, the photoresistmaterial is utilized to create the patterned mask 106 to define the fin103. As such, the patterned mask 106 may be formed to have a first widthW₁ of between about 10 nm and about 100 nm, such as about 20 nm.

Once the patterned mask 106 has been formed, the fin 103 may be formedusing a subtractive etching process along with the patterned mask 106.For example, exposed portions of the substrate 101 may be etched to formthe fin 103 from the substrate 101. In an embodiment the substrate 101may be etched by, for example, HBr/O₂, HBr/Cl₂/O₂, or SF₆/C₁₂ plasma. Inan embodiment the fin 103 may be patterned such that it will eventuallybe used for a channel in a semiconductor device such as a fin fieldeffect transistor (FinFET).

However, as one of ordinary skill in the art will recognize, thesubtractive process described above to form the fin 103 is intended tobe illustrative and is not intended to limit the embodiments. Rather,any suitable process, such as an epitaxial growth process using thesubstrate 101 and a mask, may alternatively be utilized to form the fin103. Any suitable process for forming the fin 103 from the substrate 101may be utilized, and all such processes are fully intended to beincluded within the scope of the embodiments.

FIG. 1B illustrates a close-up but not to scale view of a portion of theintersection between the fin 103 and the first masking layer 105illustrated in the dashed box 109 in FIG. 1A. As can be seen, in anembodiment in which the fin 103 is silicon and the first masking layer105 is silicon nitride, the fin 103 has first terminal groups(represented in FIG. 1B by the dashed circle labeled 111) that comprisebonds between silicon atoms and hydrogen atoms, while the first maskinglayer 105 has second terminal groups (represented in FIG. 1B by thedashed circle labeled 113) that are different from the first terminalgroups 111 and which comprise bonds between silicon atoms and nitrogenatoms. These different terminal groups can cause an undesired differencein a subsequent deposition process, and can cause undesired differencesin the thickness of a deposited material.

FIG. 2 illustrates a treatment and deposition system 200 that may beutilized to receive precursor materials from a first precursor deliverysystem 205, a second precursor delivery system 206, and a thirdprecursor delivery system 208, treat the fin 103 and/or the firstmasking layer 105, and to form layers of materials onto the substrate101, the fin 103, and the first masking layer 105 after the substrate101, the fin 103 and/or the first masking layer 105 have been treated.In an embodiment the first precursor delivery system 205, the secondprecursor delivery system 206, and the third precursor delivery system208 may work in conjunction with one another to supply the variousdifferent precursor materials to a treatment and deposition chamber 203wherein the substrate 101 (and consequently the fin 103 and the firstmasking layer 105) are placed. However, the first precursor deliverysystem 205, the second precursor delivery system 206, and the thirdprecursor delivery system 208 may have physical components that aresimilar with each other.

For example, the first precursor delivery system 205, the secondprecursor delivery system 206, and the third precursor delivery system208 may each include a gas supply 207 and a flow controller 209 (labeledin FIG. 2 with regards to the first precursor delivery system 205 butnot labeled for clarity with respect to the second precursor deliverysystem 206 and the third precursor delivery system 208). In anembodiment in which the first treatment precursor is stored in a gaseousstate, the gas supply 207 may supply the first treatment precursor tothe treatment and deposition chamber 203. The gas supply 207 may be avessel, such as a gas storage tank, that is located either locally tothe treatment and deposition chamber 203 or else may be located remotelyfrom the treatment and deposition chamber 203. Alternatively, the gassupply 207 may be a facility that independently prepares and deliversthe first treatment precursor to the flow controller 209. Any suitablesource for the first treatment precursor may be utilized as the gassupply 207, and all such sources are fully intended to be includedwithin the scope of the embodiments.

The gas supply 207 may supply the desired precursor to the flowcontroller 209. The flow controller 209 may be utilized to control theflow of the precursor to the precursor gas controller 213 and,eventually, to the treatment and deposition chamber 203, thereby alsohelping to control the pressure within the treatment and depositionchamber 203. The flow controller 209 may be, e.g., a proportional valve,a modulating valve, a needle valve, a pressure regulator, a mass flowcontroller, combinations of these, or the like. However, any suitablemethod for controlling and regulating the flow of the carrier gas to theprecursor canister 211 may be utilized, and all such components andmethods are fully intended to be included within the scope of theembodiments.

However, as one of ordinary skill in the art will recognize, while thefirst precursor delivery system 205, the second precursor deliverysystem 206, and the third precursor delivery system 208 have beendescribed herein as having identical components, this is merely anillustrative example and is not intended to limit the embodiments in anyfashion. Any type of suitable precursor delivery system, with any typeand number of individual components identical to or different from anyof the other precursor delivery systems within the treatment anddeposition system 200, may alternatively be utilized. All such precursorsystems are fully intended to be included within the scope of theembodiments.

Additionally, in an embodiment in which the first treatment precursor isstored in a solid or liquid state, the gas supply 207 may store acarrier gas and the carrier gas may be introduced into a precursorcanister (not separately illustrated), which stores the first treatmentprecursor in the solid or liquid state. The carrier gas is then used topush and carry the first treatment precursor as it either evaporates orsublimates into a gaseous section of the precursor canister before beingsent to the precursor gas controller 213. Any suitable method andcombination of units may be utilized to provide the first treatmentprecursor, and all such combination of units are fully intended to beincluded within the scope of the embodiments.

The first precursor delivery system 205, the second precursor deliverysystem 206, and the third precursor delivery system 208 may supply theirindividual precursor materials into a precursor gas controller 213. Theprecursor gas controller 213 connects and isolates the first precursordelivery system 205, the second precursor delivery system 206, and thethird precursor delivery system 208 from the treatment and depositionchamber 203 in order to deliver the desired precursor materials to thetreatment and deposition chamber 203. The precursor gas controller 213may include such devices as valves, flow meters, sensors, and the liketo control the delivery rates of each of the precursors, and may becontrolled by instructions received from the control unit 215 (describedfurther below with respect to FIG. 3).

The precursor gas controller 213, upon receiving instructions from thecontrol unit 215, may open and close valves so as to connect one of thefirst precursor delivery system 205, the second precursor deliverysystem 206, and the third precursor delivery system 208 to the treatmentand deposition chamber 203 and direct a desired precursor materialthrough a manifold 216, into the treatment and deposition chamber 203,and to a showerhead 217. The showerhead 217 may be utilized to dispersethe chosen precursor material into the treatment and deposition chamber203 and may be designed to evenly disperse the precursor material inorder to minimize undesired process conditions that may arise fromuneven dispersal. In an embodiment the showerhead 217 may have acircular design with openings dispersed evenly around the showerhead 217to allow for the dispersal of the desired precursor material into thetreatment and deposition chamber 203.

However, as one of ordinary skill in the art will recognize, theintroduction of precursor materials to the treatment and depositionchamber 203 through a single showerhead 217 or through a single point ofintroduction as described above is intended to be illustrative only andis not intended to be limiting to the embodiments. Any number ofseparate and independent showerheads 217 or other openings to introduceprecursor materials into the treatment and deposition chamber 203 mayalternatively be utilized. All such combinations of showerheads andother points of introduction are fully intended to be included withinthe scope of the embodiments.

The treatment and deposition chamber 203 may receive the desiredprecursor materials and expose the precursor materials to the substrate101, the fin 103, and the first masking layer 105, and the treatment anddeposition chamber 203 may be any desired shape that may be suitable fordispersing the precursor materials and contacting the precursormaterials with the substrate 101, the fin 103, and the first maskinglayer 105. In the embodiment illustrated in FIG. 2, the treatment anddeposition chamber 203 has a cylindrical sidewall and a bottom. However,the treatment and deposition chamber 203 is not limited to a cylindricalshape, and any other suitable shape, such as a hollow square tube, anoctagonal shape, or the like, may be utilized. Furthermore, thetreatment and deposition chamber 203 may be surrounded by a housing 219made of material that is inert to the various process materials. Assuch, while the housing 219 may be any suitable material that canwithstand the chemistries and pressures involved in the depositionprocess, in an embodiment the housing 219 may be steel, stainless steel,nickel, aluminum, alloys of these, combinations of these, and like.

Within the treatment and deposition chamber 203 the substrate 101 may beplaced on a mounting platform 221 in order to position and control thesubstrate 101 and the fin 103 during the treatment and depositionprocesses. The mounting platform 221 may include heating mechanisms inorder to heat the substrate 101 during the treatment and depositionprocesses. Furthermore, while a single mounting platform 221 isillustrated in FIG. 2, any number of mounting platforms 221 mayadditionally be included within the treatment and deposition chamber203.

Additionally, the treatment and deposition chamber 203 and the mountingplatform 221 may be part of a cluster tool system (not shown). Thecluster tool system may be used in conjunction with an automatedhandling system in order to position and place the substrate 101 intothe treatment and deposition chamber 203 prior to the treatment anddeposition processes, position, hold the substrate 101 during thetreatment and deposition processes, and remove the substrate 101 fromthe treatment and deposition chamber 203 after the treatment anddeposition processes.

The treatment and deposition chamber 203 may also have an exhaust outlet225 for exhaust gases to exit the treatment and deposition chamber 203.A vacuum pump 223 may be connected to the exhaust outlet 225 of thetreatment and deposition chamber 203 in order to help evacuate theexhaust gases. The vacuum pump 223, under control of the control unit215, may also be utilized to reduce and control the pressure within thetreatment and deposition chamber 203 to a desired pressure and may alsobe utilized to evacuate precursor materials from the treatment anddeposition chamber 203 in preparation for the introduction of the nextprecursor material.

FIG. 3 illustrates an embodiment of the control unit 215 that may beutilized to control the precursor gas controller 213 and the vacuum pump223 (as illustrated in FIG. 2). The control unit 215 may be any form ofcomputer processor that can be used in an industrial setting forcontrolling process machines. In an embodiment the control unit 215 maycomprise a processing unit 201, such as a desktop computer, aworkstation, a laptop computer, or a dedicated unit customized for aparticular application. The control unit 215 may be equipped with adisplay 303 and one or more input/output components 305, such asinstruction outputs, sensor inputs, a mouse, a keyboard, printer,combinations of these, or the like. The processing unit 301 may includea central processing unit (CPU) 306, memory 308, a mass storage device310, a video adapter 314, and an I/O interface 316 connected to a bus312.

The bus 312 may be one or more of any type of several bus architecturesincluding a memory bus or memory controller, a peripheral bus, or videobus. The CPU 306 may comprise any type of electronic data processor, andthe memory 308 may comprise any type of system memory, such as staticrandom access memory (SRAM), dynamic random access memory (DRAM), orread-only memory (ROM). The mass storage device 310 may comprise anytype of storage device configured to store data, programs, and otherinformation and to make the data, programs, and other informationaccessible via the bus 312. The mass storage device 310 may comprise,for example, one or more of a hard disk drive, a magnetic disk drive, oran optical disk drive.

The video adapter 314 and the I/O interface 316 provide interfaces tocouple external input and output devices to the processing unit 301. Asillustrated in FIG. 3, examples of input and output devices include thedisplay 303 coupled to the video adapter 314 and the I/O component 305,such as a mouse, keyboard, printer, and the like, coupled to the I/Ointerface 316. Other devices may be coupled to the processing unit 301,and additional or fewer interface cards may be utilized. For example, aserial interface card (not shown) may be used to provide a serialinterface for a printer. The processing unit 301 also may include anetwork interface 318 that may be a wired link to a local area network(LAN) or a wide area network (WAN) 320 and/or a wireless link.

It should be noted that the control unit 215 may include othercomponents. For example, the control unit 215 may include powersupplies, cables, a motherboard, removable storage media, cases, and thelike. These other components, although not shown in FIG. 3, areconsidered part of the control unit 215.

FIGS. 4A-4B illustrate a first treatment (represented in FIG. 4A by thewavy lines labeled 401) of the fin 103 and the substrate 101 inpreparation for a deposition of a first dielectric layer 501 (notillustrated in FIGS. 4A-4B but illustrated and described further belowwith respect to FIGS. 6A-6B) onto the substrate 101 and also onto thefin 103, the first masking layer 105, and the second masking layer 107.In an embodiment the first treatment 401 may be performed within thetreatment and deposition chamber 203 (although it may also be performedin a separate chamber than the chamber used to deposit the firstdielectric layer 501) and may be initiated by placing a first treatmentprecursor chemical within the third precursor delivery system 208. Thefirst treatment precursor chemical may be a chemical that will reactwith the material of the substrate 101 and the fin 103 (e.g. silicon)and modify the first terminal groups 111 of the substrate 101 and thefin 103 to be the same as the second terminal groups 113 on the firstmasking layer 105. In an embodiment in which the fin 103 and thesubstrate 101 are silicon and the masking layer is silicon nitride, thefirst treatment precursor chemical may be NF₃, although any othersuitable chemical, such as NH₃ or N₂O, may also be used either by itselfor in combination.

Once the first treatment precursor chemical has been placed into thethird precursor delivery system 208, the first treatment 401 may beinitiated by the control unit 215 sending an instruction to theprecursor gas controller 213 to connect the third precursor deliverysystem 208 to the treatment and deposition chamber 203. Once connected,the third precursor delivery system 208 can deliver the first treatmentprecursor chemical (e.g., the NF₃) to the showerhead 217 through theprecursor gas controller 213 and the manifold 216. The showerhead 217can then disperse the first treatment precursor chemical into thetreatment and deposition chamber 203, wherein the first treatmentprecursor chemical can react to the exposed surfaces of the substrate101 and the fin 103.

In the embodiment to treat the substrate 101 and the fin 103 made ofsilicon with NF₃, the first treatment precursor chemical may be flowedinto the treatment and deposition chamber 203 at a flow rate of betweenabout 1 slm and about 5 slm for about 24 seconds. Additionally, thetreatment and deposition chamber 203 may be held at a pressure ofbetween about 1 mtorr and about 5 mtorr, such as about 2 mtorr, and atemperature of between about 200° C. and about 300° C., such as about250° C. However, as one of ordinary skill in the art will recognize,these process conditions are only intended to be illustrative, as anysuitable process conditions may be utilized while remaining within thescope of the embodiments.

Looking at FIG. 4B (which illustrates a close-up but still not to scaleview of the dashed box 109 in FIG. 4A), the first treatment precursorchemical of the first treatment 401 will react with the exposed firstterminal groups 111 of the fin 103 and the substrate 101 withoutsignificantly reacting with the second terminal groups 113 of the firstmasking layer 105. In particular, in an embodiment in which NF₃ isutilized as the first treatment precursor chemical, the NF₃ will reactwith the silicon portion of the fin 103, breaking the bonds within thefirst terminal groups 111 between the silicon and the hydrogen andremoving the terminal hydrogen atom. Once the terminal hydrogen atom hasbeen removed, the now open terminal site at the surface of the fin 103will bond with the nitrogen atoms to form a third terminal group(represented in FIG. 4B by the dashed circle labeled 403) thatcomprises, e.g., a SiNF₂ compound.

FIG. 4C illustrates the next step in the reaction mechanism of theembodiment wherein the fin 103 is silicon and is treated with NF₃. Inthis step the two fluorine atoms disassociate from the nitrogen atombonded to the silicon. In an embodiment the fluorine atoms willdisassociate spontaneously as part of the reactions that occur duringthe first treatment 401, and will leave behind an open nitrogen atom aspart of a fourth terminal group (represented in FIG. 4C by the dashedcircle labeled 405) on the silicon of the fin 103.

However, by modifying the first terminal groups 111 (e.g., siliconbonded to hydrogen) at the surface of the fin 103 into the fourthterminal groups 405 (e.g., silicon bonded to nitrogen), the surface ofthe fin 103 now has terminal groups that are the same as or similar tothe first masking layer 105. As such, during the subsequent depositionprocess (described further below with respect to FIG. 5), both the fin103 and the first masking layer 105 have similar terminal groups andwill react in a similar fashion.

FIG. 5a illustrates a deposition of the first dielectric layer 501 overthe fin 103, the first masking layer 105, and the second masking layer107. In an embodiment the same treatment and deposition system 200 maybe utilized to deposit the first dielectric layer 501 onto the fin 103,the first masking layer 105, and the second masking layer 107. In anembodiment the first dielectric layer 501 may be a dielectric layer of amaterial such as silicon nitride. The first dielectric layer 501 may beformed in the treatment and deposition chamber 203 utilizing adeposition process such as atomic layer deposition (ALD). However, thismaterial and this process are intended to be illustrative and are notintended to be limiting, as other desirable materials, such as otherdielectric materials, and other suitable deposition processes, mayalternatively be utilized.

In an embodiment the formation of the first dielectric layer 501 may beinitiated by putting a first precursor material into the first precursordelivery system 205. For example, in an embodiment in which the firstdielectric layer 501 is silicon nitride, the first precursor materialmay be a precursor such as dichlorosilane and may be placed into thefirst precursor delivery system 205. However, as one of ordinary skillin the art will recognize, this precursor is not the only precursor thatmay be utilized to form a layer of silicon nitride, and the use ofdichlorosilane is not intended to be limiting to the embodiments. Anysuitable precursor material in any suitable phase (solid, liquid, orgas) to form a layer of silicon nitride, such as monochlorosilane, orany other precursor that may be used to form alternative layers, may beutilized.

Additionally, a second precursor material may be placed into the secondprecursor delivery system 206. In the embodiment in which a layer ofsilicon nitride is the desired material for the first dielectric layer501, the second precursor material may be a precursor material that maycontain nitrogen in order to react with the first precursor material toform a monolayer of silicon nitride. For example, in the embodiment inwhich dichlorosilane is utilized as the first precursor material,ammonia (NH₃) may be used as the second precursor material and may beplaced into the second precursor delivery system 206. However, thedescription of ammonia as the second precursor material is not intendedto be limiting to the embodiments, and any other suitable precursormaterial, such as N₂, combinations of these, or the like, mayalternatively be utilized as the second precursor material.

Once the first precursor material and the second precursor material havebeen placed into the first precursor delivery system 205 and the secondprecursor delivery system 206, respectively, the formation of the firstdielectric layer 501 may be initiated by the control unit 215 sending aninstruction to the precursor gas controller 213 to connect the firstprecursor delivery system 205 to the treatment and deposition chamber203. Once connected, the first precursor delivery system 205 can deliverthe first precursor material (e.g., the dichlorosilane) to theshowerhead 217 through the precursor gas controller 213 and the manifold216. The showerhead 217 can then disperse the first precursor materialinto the treatment and deposition chamber 203, wherein the firstprecursor material can be adsorbed and react to the exposed surfaces ofthe substrate 101, the fin 103, the first masking layer 105, and thesecond masking layer 107.

In the embodiment to form a layer of silicon nitride, the firstprecursor material may be flowed into the treatment and depositionchamber 203 at a flow rate of between about 1 slm and about 5 slm forabout 50 second per cycle. Additionally, the treatment and depositionchamber 203 may be held at a pressure of between about 3 torr and about5 torr, such as about 4 torr, and a temperature of between about 450° C.and about 700° C., such as about 550° C. However, as one of ordinaryskill in the art will recognize, these process conditions are onlyintended to be illustrative, as any suitable process conditions may beutilized while remaining within the scope of the embodiments.

As the first precursor material is adsorbed onto the substrate 101, thefin 103, the first masking layer 105, and the second masking layer 107,the first precursor material will react with open active sites locatedon the exposed surfaces of the substrate 101, the fin 103, the firstmasking layer 105, and the second masking layer 107. However, once allof the open active sites on the substrate 101, the fin 103, the firstmasking layer 105, and the second masking layer 107 have reacted withthe first precursor material, the reaction will stop, as there are nomore open active sites to which the first precursor material will bond.This limitation causes the reaction of the first precursor material withthe substrate 101, the fin 103, the first masking layer 105, and thesecond masking layer 107 to be self-limiting and to form a monolayer ofthe reacted first precursor material on the surface of the fin 103,thereby allowing for a more precise control of the thickness of thefirst dielectric layer 501.

FIG. 5B illustrates a particular embodiment in which the first precursormaterial is dichlorosilane which has two hydrogen atoms and two chlorineatoms all bonded to the same silicon atom. In this embodiment one of thechlorine atoms will react with one of the hydrogen atoms (that hasbonded to the open nitrogen sites present in FIG. 4C) and the nitrogenwill bond with the silicon atom within the dichlorosilane. As such, thesilicon atom is bonded to the nitrogen atom.

After the self-limiting reaction on the fin 103 has finished, thetreatment and deposition chamber 203 may be purged of the firstprecursor material. For example, the control unit 215 may instruct theprecursor gas controller 213 to disconnect the first precursor deliverysystem 205 (containing the first precursor material to be purged fromthe treatment and deposition chamber 203) and to connect a purge gasdelivery system 214 to deliver a purge gas to the treatment anddeposition chamber 203. In an embodiment the purge gas delivery system214 may be a gaseous tank or other facility that provides a purge gassuch as nitrogen, argon, xenon, or other non-reactive gas to thetreatment and deposition chamber 203. Additionally, the control unit 215may also initiate the vacuum pump 223 in order to apply a pressuredifferential to the treatment and deposition chamber 203 to aid in theremoval of the first precursor material. The purge gas, along with thevacuum pump 223, may purge the first precursor material from thetreatment and deposition chamber 203 for about 3 seconds.

After the purge of the first precursor material has been completed, theintroduction of the second precursor material (e.g., ammonia) to thetreatment and deposition chamber 203 may be initiated by the controlunit 215 sending an instruction to the precursor gas controller 213 todisconnect the purge gas delivery system 214 and to connect the secondprecursor delivery system 206 (containing the second precursor material)to the treatment and deposition chamber 203. Once connected, the secondprecursor delivery system 206 can deliver the second precursor materialto the showerhead 217. The showerhead 217 can then disperse the secondprecursor material into the treatment and deposition chamber 203,wherein the second precursor material can be adsorbed on the surfaces ofthe substrate 101, the fin 103, the first masking layer 105, and thesecond masking layer 107 and react with the first precursor material inanother self-limiting reaction to form a monolayer of the desiredmaterial, e.g., silicon nitride, on the surface of the substrate 101,the fin 103, the first masking layer 105, and the second masking layer107.

In the embodiment discussed above to form a layer of silicon nitridewith dichlorosilane, the ammonia may be introduced into the treatmentand deposition chamber 203 at a flow rate of between about 2 slm andabout 10 slm, such as about 5 slm, for about 30 seconds. Additionally,the treatment and deposition chamber 203 may be held at a pressure ofabout 0 torr and a temperature of between about 450° C. and about 700°C. However, as one of ordinary skill in the art will recognize, theseprocess conditions are only intended to be illustrative, as any suitableprocess conditions may be utilized to introduce oxygen while remainingwithin the scope of the embodiments.

After the monolayer of the desired material, e.g., silicon nitride, hasbeen formed, the treatment and deposition chamber 203 may be purged(leaving behind the monolayer of the desired material on the substrate101, the fin 103, the first masking layer 105, and the second maskinglayer 107) using, e.g., a purge gas from the purge gas delivery system214 for about three seconds. After the treatment and deposition chamber203 has been purged, a first cycle for the formation of the desiredmaterial has been completed, and a second cycle similar to the firstcycle may be started. For example, the repeated cycle may introduce thefirst precursor material, purge with the purge gas, pulse with thesecond precursor, and purge with the purge gas. These cycles may berepeated until the first dielectric layer 501 on the fin 103 has afourth thickness T₄ of between about 40 Å and about 60 Å, such as about50 Å. Once the desired thickness of the first dielectric layer 501 hasbeen reached, the substrate 101 may be removed from the treatment anddeposition chamber 203 for further processing.

However, as one of ordinary skill in the art will recognize, the abovedescribed process to form the first dielectric layer 501 is intended tobe illustrative and is not intended to be limiting to the embodiments.Any other suitable process, such as initially pulsing the secondprecursor material (e.g., ammonia), purging with the purge gas,introducing the first precursor material (e.g., dichlorosilane), andpurging with the purge gas to complete a first cycle and then repeatingthe first cycle, may alternatively be utilized. This and any othersuitable process to form the first dielectric layer 501 are fullyintended to be included within the scope of the embodiments.

However, by using the first treatment 401 prior to the deposition of thefirst dielectric layer 501, the terminal groups at the surface of boththe fin 103 (e.g., the fourth terminal groups 405) and the terminalgroups at the surface of the first masking layer 105 (e.g., the secondterminal groups 113) will be almost the same (as illustrated in FIG. 4Cat the end of the first treatment 401) instead of being different (asillustrated in FIG. 1B prior to the first treatment 401). As such,similar reactions will occur at a similar reaction rate on both the fin103 and the first masking layer 105, and any differences that may occurbecause of the different reactions or reaction rates may be reduced oreliminated. As such, the thickness of the first dielectric layer 501 maybe constant as the first dielectric layer 501 transfers from over thefin 103 to over the first masking layer 105, and a more uniformdeposition may be obtained.

FIG. 5C illustrates this effect. In particular, the original firstterminal groups 111 that terminate the material of the fin 103 (e.g.,the silicon-hydrogen bonds illustrated by the dashed circle 503 on thebaseline (BSL)) will have a cycle growth rate (in A/cycle) of over 1.0Å/cycle. However, by performing the first treatment 401, the firstterminal groups 111 may be modified to the fourth terminal groups 405(e.g., the silicon-nitrogen bonds illustrated by the dashed circle 505),which have a similar cycle growth rate as the second terminal groups 113(e.g., the silicon-nitrogen bonds illustrated by the dashed circlelabeled 507) that terminate the material of the first masking layer 105(e.g., silicon nitride). As such, a more consistent growth rate may beobtained, and a more consistent thickness may be obtained whendepositing the first dielectric layer 501 over separate materials.

Additional data is presented in FIG. 5D, which illustrates XPS datataken before the first treatment 401 (represented in FIG. 5D by thelines labeled 507), after the first treatment 401 (represented in FIG.5D by the lines labeled 509), and after the deposition of the firstdielectric layer 501 (represented in FIG. 5D by the line labeled 511)for both the fin 103 (e.g., silicon substrate) and the first maskinglayer 105 (e.g., silicon nitride substrate). As can be seen, prior tothe first treatment 401, the fin 103 has mostly silicon-hydrogen bondsand almost no silicon-nitrogen bonds or fluorine while the first maskinglayer 105 has primarily silicon-nitrogen bonds. However, after the firsttreatment 401, the fin 103 has a combination of silicon-nitrogen bondsas well as silicon-fluorine bonds while the first masking layer 105still has primarily silicon-nitrogen bonds, although there is ameasurable presence of fluorine. Finally, after the deposition of thefirst dielectric layer 501, the fin 103 has primarily silicon-nitrogenbonds while the first masking layer 107 still has primarily thesilicon-nitrogen bonds.

FIGS. 6A-6C illustrate another embodiment in which a second treatment701 (not illustrated in FIGS. 6A-6C but illustrated and described belowwith respect to FIGS. 7A-7C) may be utilized to modify the growth rateof the first dielectric layer 501 over differing materials, with FIG. 6Billustrating a surface of the substrate 101 within the dashed box 603 inFIG. 6A and with FIG. 6C illustrating a surface of spacers 601 withinthe dashed box 605 in FIG. 6A. In this embodiment, the first treatmentis not performed and, prior to the second treatment 701 being performed,the spacers 601 may be formed adjacent to the fin 103, the first maskinglayer 105, and the second masking layer 107. The spacers 601 may beformed on opposing sides of the fin 103, and may be formed by blanketdepositing a spacer layer (not separately illustrated) on the previouslyformed structure. The spacer layer may comprise SiN, SiCN, SiOCN, andthe like and may be formed by methods utilized to form such a layer,such as chemical vapor deposition (CVD), plasma enhanced CVD, sputter,and other methods known in the art. The spacers 601 may then bepatterned, such as by one or more etches to remove the spacer layer fromthe horizontal surfaces of the structure.

In this embodiment the surface of the substrate 101 may be exposed forthe subsequent deposition of the first dielectric layer 501, and maycomprise different terminal groups from the spacers 601. For example, asillustrated in FIG. 6B, in an embodiment in which the substrate 101 issilicon, the substrate 101 may have the first terminal groups 111wherein silicon atoms are bonded to hydrogen atoms. However, asillustrated in FIG. 6C, in an embodiment in which the spacers 601comprise silicon nitride, the spacers 601 may have exposed surfaces withfifth terminal groups (represented in FIG. 6C by the dashed circlelabeled 607) that comprise silicon bonded with nitrogen.

FIGS. 7A-7C illustrate that, after the spacers 601 have been formed, thesecond treatment (represented in FIG. 7A by the wavy lines labeled 701)may be used to increase the selectivity of growth between the spacers601 and the substrate 101 in order to have a thicker deposition of thefirst dielectric layer 501 over the substrate 101 than over the spacers601. In an embodiment the second treatment 701 may be performed withinthe treatment and deposition chamber 203 and may be initiated by placinga second treatment precursor chemical (instead of the first treatmentprecursor chemical) within the third precursor delivery system 208. Thesecond treatment precursor chemical may be a chemical that will reactwith the first terminal groups 111 of the material of the substrate 101and modify the first terminal groups 111 into sixth terminal groups(represented in FIG. 7B by the dashed circle labeled 703), which maycomprise, e.g., silicon atoms bonded to oxygen atoms. In an embodimentin which the fin 103 and the substrate 101 are silicon and the spacers601 are silicon nitride, the second treatment precursor chemical may bean oxygen containing precursor, such as O₂, N₂O, combinations of these,or the like, although any other suitable chemical may also be usedeither by itself or in combination. In an embodiment the secondtreatment precursor chemical is not a plasma so as to avoid excessivereactions with the fifth terminal groups 607.

Once the second treatment precursor chemical has been placed into thethird precursor delivery system 208, the second treatment 701 may beinitiated by the control unit 215 sending an instruction to theprecursor gas controller 213 to connect the third precursor deliverysystem 208 to the treatment and deposition chamber 203. Once connected,the third precursor delivery system 208 can deliver the second treatmentprecursor chemical (O₂) to the showerhead 217 through the precursor gascontroller 213 and the manifold 216. The showerhead 217 can thendisperse the second treatment precursor chemical into the treatment anddeposition chamber 203, wherein the second treatment precursor chemicalcan react with the exposed first terminal groups 111 of the substrate101.

In the embodiment to treat the substrate 101 and the fin 103 made ofsilicon with O₂, the second treatment precursor chemical may be flowedinto the treatment and deposition chamber 203 at a flow rate of betweenabout 0.2 slm and about 0.5 slm for about 600 seconds. Additionally, thetreatment and deposition chamber 203 may be held at a pressure ofbetween about 750 torr and about 770 torr, such as about 760 torr, and atemperature of between about 20° C. and about 60° C., such as about 25°C. However, as one of ordinary skill in the art will recognize, theseprocess conditions are only intended to be illustrative, as any suitableprocess conditions may be utilized while remaining within the scope ofthe embodiments.

FIG. 7B illustrates a result of the second treatment 701 at the surfaceof the substrate 101. In an embodiment in which the substrate 101 issilicon and the second treatment precursor is oxygen, the first terminalgroups 111 of hydrogen bonded to the silicon have been modified orreplaced during the second treatment 701 with the sixth terminal groups703 of oxygen bonded to the silicon. As such, the bond dissociationenergy of the terminal groups at the surface of the substrate 101 arechanged from 298 kJ/mol (for hydrogen bonded to silicon) to 798 kJ/mol(for oxygen bonded to silicon), which moves from below the bonddissociation energy of 439 kJ/mol (for nitrogen bonded to the silicon)for the fifth terminal groups 607 of the spacers 601 to above the fifthterminal groups 607 of the spacers 601.

FIG. 7C illustrates a result of the second treatment 701 at the surfaceof the spacers 601. In an embodiment in which the spacers 601 aresilicon nitride and the second treatment precursor is oxygen, the fifthterminal groups 607 of nitrogen bonded to the silicon is minimallyaffected, if at all, by the second treatment 701. As such, the fifthterminal groups 607 of nitrogen bonded to the silicon remain while thefirst terminal groups 111 of the substrate 101 are modified to the sixthterminal groups 703 by the second treatment 701.

FIGS. 8A-8B illustrate the deposition of the first dielectric layer 501onto the substrate 101 and the spacers 601 after the second treatment701. In an embodiment the first dielectric layer 501 may be siliconnitride and may be deposited as described above with respect to FIG. 5.For example, the substrate 101 and spacers 601 may be placed within thetreatment and deposition chamber 203 and the control unit 215 willutilize the precursor gas controller 213 to sequentially introduce thefirst precursor material, purge the treatment and deposition chamber203, introduce the second precursor material, purge the treatment anddeposition chamber 203, and repeat the process to build up successivemonolayers of material to form the first dielectric layer 501.

However, because the second treatment 701 has been used to modify thefirst terminal groups 111 of the substrate 101 into the sixth terminalgroups 703, the first dielectric layer 501 will have a larger rate ofgrowth at the surface of the substrate 101 than at the surface of thespacers 601. As such, the portion of the first dielectric layer 501grown on the substrate 101 may have a fifth thickness T₅ of betweenabout 43 Å and about 57 Å, such as about 45 Å, while the firstdielectric layer 501 may have a sixth thickness T₆ of between about 48 Åand about 52 Å, such as about 50 Å, adjacent to the spacers 601. Such aselective deposition may be achieved without the use ofphotolithographical processes.

FIG. 8B illustrates a chart showing that the growth rate of thesubstrate 101 with the first terminal groups 111 (represented in FIG. 8Bby the circle labeled 801 at the baseline (BSL)) may be modified to alarger/smaller growth rate by modifying the first terminal groups 111 tothe sixth terminal groups 703. As such, the first dielectric layer 501may have the larger thickness over the substrate 101 than adjacent tothe spacers 601 without the use of additional photolithographyprocesses. FIG. 8B additionally illustrates the growth rates after aplasma treatment utilizing oxygen or and a thermal oxidation process,which illustrate an even smaller growth rate.

FIG. 8C illustrates a chart of test data illustrating the selectivity ofthe second treatment 701 using an XPS process to chart the substrate 101and the spacers 601. In particular, using a long-Q treatment, such as bytreating the wafer in a condition such as oxygen gas at room temperatureand one atmosphere for a long time such as 6 hours, for the oxidation asdescribed above with respect to the second treatment process 701, thematerial of the substrate 101 will be modified to include oxygen bondedto silicon while the material of the spacers 601 is not modified. Assuch, the modification may be performed on the substrate 101 withoutsignificant modifications occurring on the spacers 601.

FIGS. 9A-9C illustrate yet another embodiment in which a third treatment(represented in FIG. 9A by the wavy lines labeled 901) is utilized toform a greater selectivity of growth on the substrate 101, with FIG. 9Billustrating a surface of the substrate 101 within the dashed box 903 inFIG. 9A and with FIG. 9C illustrating a surface of the spacers 601within the dashed box 905 in FIG. 9A. In this embodiment the spacers 601have been formed adjacent to the fin 103 prior to the third treatment901, and the spacers 601 may be as described above with respect to FIGS.6A-6C. In particular the substrate 101 may have the first terminalgroups 111 (not separately illustrated in FIGS. 9A-9C) that comprisesilicon bonded to hydrogen while the spacers 601 have the fifth terminalgroups 607 that comprise silicon bonded to nitrogen.

In an embodiment the third treatment 901 may be performed within thetreatment and deposition chamber 203 and may be initiated by placing athird treatment precursor chemical (instead of the first treatmentprecursor chemical or the second treatment precursor chemical) withinthe third precursor delivery system 208. The third treatment precursorchemical may be a chemical that will react with the first terminalgroups 111 of the material of the substrate 101 and modify the firstterminal groups 111 into seventh terminal groups 907 which comprisefluorine atoms bonded to silicon atoms. In an embodiment in which thefin 103 and the substrate 101 are silicon and the spacers 601 aresilicon nitride, the third treatment precursor chemical may be afluorine containing precursor such as F₂, SF₆, combinations of these, orthe like, although any other suitable chemical may also be used eitherby itself or in combination.

Once the third treatment precursor chemical has been placed into thethird precursor delivery system 208, the third treatment 901 may beinitiated by the control unit 215 sending an instruction to theprecursor gas controller 213 to connect the third precursor deliverysystem 208 to the treatment and deposition chamber 203. Once connected,the third precursor delivery system 208 can deliver the third treatmentprecursor chemical (e.g., the F₂) to the showerhead 217 through theprecursor gas controller 213 and the manifold 216. The showerhead 217can then disperse the third treatment precursor chemical into thetreatment and deposition chamber 203, wherein the third treatmentprecursor chemical can react to the exposed first terminal groups 111 ofthe surface of the substrate 101.

In the embodiment to treat the first terminal groups 111 of thesubstrate 101 and the fin 103 made of silicon with F₂, the thirdtreatment precursor chemical may be flowed into the treatment anddeposition chamber 203 at a flow rate of between about 1 slm and about 3slm for about 600 second. Additionally, the treatment and depositionchamber 203 may be held at a pressure of about 0 torr, and a temperatureof between about 400° C. and about 500° C., such as about 450° C.However, as one of ordinary skill in the art will recognize, theseprocess conditions are only intended to be illustrative, as any suitableprocess conditions may be utilized while remaining within the scope ofthe embodiments.

FIG. 9B illustrates a result of the third treatment 901 at the surfaceof the substrate 101. In an embodiment in which the first terminalgroups 111 at the surface of the substrate 101 comprise silicon bondedto hydrogen and the third treatment precursor is fluorine, the firstterminal group 111 of hydrogen bonded to the silicon has been modifiedduring the third treatment 901 into the seventh terminal groups 907which comprise fluorine atoms bonded to silicon atoms. As such, the bonddissociation energy at the terminal groups at the surface of thesubstrate 101 changes from 298 kJ/mol (for the first terminal groups 111of hydrogen bonded to silicon) to 565 kJ/mol (for the seventh terminalgroups 907 of fluorine bonded to silicon), which moves the bonddissociation energy from below the bond dissociation energy of 439kJ/mol of the fifth terminal groups 607 (for nitrogen bonded to thesilicon on the spacers 601) to above the bond dissociation energy of thefifth terminal groups 607 of the spacers 601.

FIG. 9C illustrates a result of the third treatment 901 at the surfaceof the spacers 601. In an embodiment in which the spacers 601 aresilicon nitride and the third treatment precursor is fluorine, the fifthterminal group 607 of nitrogen bonded to the silicon is minimallyaffected, if at all, by the third treatment 901. As such, the fifthterminal groups 607 of nitrogen bonded to the silicon remain while thefirst terminal groups 111 at the surface of the substrate 101 areadjusted by the third treatment 901.

FIGS. 10A-10B illustrate the deposition of the first dielectric layer501 onto the substrate 101 and the spacers 601 after the third treatment901. In an embodiment the first dielectric layer 501 may be siliconnitride and may be deposited as described above with respect to FIG. 5.For example, the substrate 101 and spacers 601 may be within thetreatment and deposition chamber 203 and the control unit 215 willutilize the precursor gas controller 213 to sequentially introduce thefirst precursor material, purge the treatment and deposition chamber203, introduce the second precursor material, purge the treatment anddeposition chamber 203, and repeat the process to build up successivemonolayers of material to form the first dielectric layer 501.

However, because the third treatment 901 has been used to modify thefirst terminal groups 111 of the substrate 101 into the seventh terminalgroups 907, the first dielectric layer 501 will grow at a slower rate ofgrowth (or will not grow at all) on the surface of the substrate 101than at the surface of the spacers 601. As such, the portion of thefirst dielectric layer 501 grown on the substrate 101 may have a sevenththickness T₇ of less than about 10 Å, such as about 0 Å, while the firstdielectric layer 501 may have an eighth thickness T₈ of between about 48Å and about 52 Å, such as about 50 Å, adjacent to the spacers 601.

In particular, as illustrated in FIG. 10B, the original first terminalgroups 111 that terminate the material of the substrate 101 (e.g., thesilicon-hydrogen bonds illustrated by the dashed circle 1003 on thebaseline (BSL)) will have a cycle growth rate (in A/cycle) of over 1.0Å/cycle. However, by performing the third treatment 901, the firstterminal groups 111 may be modified to the seventh terminal groups 907(e.g., the silicon-fluorine bonds illustrated by the dashed circle1005), which has a cycle growth rate of almost zero, whether it occursat the center (CTR) of the test wafer or at the edge of the test wafer(EDGE). As such, a selective deposition of the first dielectric layer501 may be obtained, wherein the first dielectric layer 501 grows on thespacers 601 but does not grow, or only minimally grows, on the substrate101, and the presence of the first dielectric layer 501 may be obtainedon the spacers 601 and not on the substrate 101 without a separatephotolithography process.

FIGS. 10C-10D illustrate additional data showing the selective growth ofsilicon nitride on a silicon substrate and spacers that have beentreated with F₂. FIG. 10C illustrates two types of treatment, one inwhich the treatment with F₂ is performed over the entire wafer(represented as Wafer Center (CTR) and represented by the line labeled1007), and one in which the treatment is performed only on the sideedges of the wafer (represented as Wafer EDGE and represented by theline labeled 1009). In an embodiment the side edges may be treated bystacking multiple wafers or dummy wafers into a wafer boat such that thetop surfaces are covered and only the side surfaces of the wafers areexposed, while the treatment over the center may be performed by placingthe wafers apart from each other such that the centers of the wafers areexposed. As can be seen, the treatment with F₂ will cause a decrease inthe number of silicon-hydrogen bonds for a U % CIP (wafer treatmentuniformity improvement) from the baseline (along with an increase in thenumber of silicon fluorine bonds).

FIG. 10D illustrates a map of both a silicon wafer (on the left handside of FIG. 10D) and a silicon nitride wafer (on the right hand side ofFIG. 10D) that have been treated with F₂ and then had a depositionprocess of silicon nitride performed. As can be seen, the siliconsubstrate shows very little if any growth of silicon nitride. However,the silicon nitride substrate shows a growth of about 40 Å. As such, thedeposition of silicon nitride may be performed selectively to thesilicon nitride material and not on the silicon material.

In accordance with an embodiment, a method of manufacturing asemiconductor device comprising forming a mask layer over and inphysical contact with a fin, wherein the fin comprises first terminalgroups and the mask layer comprises second terminal groups differentfrom the first terminal groups is provided. The first terminal groupsare treated to form third terminal groups, wherein the third terminalgroups are the same as the second terminal groups. A first depositionprecursor is introduced to the third terminal groups and the secondterminal groups and the first deposition precursor is removed from thethird terminal groups and the second terminal groups. A seconddeposition precursor different from the first deposition precursor isintroduced after the removing the first deposition precursor, whereinthe introducing the first deposition precursor and the introducing thesecond deposition precursor form a first material.

In accordance with another embodiment, a method of manufacturing asemiconductor device comprising forming a spacer over a substrate,wherein the substrate comprises a first material that has a first atomiclayer deposition growth rate and wherein the spacer comprises a secondmaterial with a second atomic layer deposition growth rate differentfrom the first atomic layer deposition growth rate is provided. Thefirst atomic layer deposition growth rate is adjusted to a third atomiclayer deposition growth rate, and a dielectric layer is deposited afterthe adjusting the first atomic layer deposition growth rate.

In accordance with yet another embodiment, a method of manufacturing asemiconductor device the method comprising depositing a second materialon a substrate, the substrate comprising a first material, the secondmaterial being different from the first material, is provided. A fin isformed from the substrate after the depositing the second material onthe substrate. The first material is treated with a first treatmentprecursor after the forming the fin, the first treatment precursormodifying a first terminal group of the first material into a secondterminal group without modifying a third terminal group of the secondmaterial. A dielectric layer is deposited on the first material and thesecond material, wherein the depositing the dielectric layer furthercomprises reacting the second terminal group and the third terminalgroup with a first deposition precursor to form a product group andreacting the product group with a second deposition precursor after thefirst deposition precursor has been removed.

The foregoing outlines features of several embodiments so that thoseskilled in the art may better understand the aspects of the presentdisclosure. Those skilled in the art should appreciate that they mayreadily use the present disclosure as a basis for designing or modifyingother processes and structures for carrying out the same purposes and/orachieving the same advantages of the embodiments introduced herein.Those skilled in the art should also realize that such equivalentconstructions do not depart from the spirit and scope of the presentdisclosure, and that they may make various changes, substitutions, andalterations herein without departing from the spirit and scope of thepresent disclosure.

What is claimed is:
 1. A method of manufacturing a semiconductor device,the method comprising: forming a spacer over a substrate, wherein thesubstrate comprises a first material that has a first atomic layerdeposition growth rate and wherein the spacer comprises a secondmaterial with a second atomic layer deposition growth rate differentfrom the first atomic layer deposition growth rate; adjusting the firstatomic layer deposition growth rate to a third atomic layer depositiongrowth rate; and depositing a dielectric layer after the adjusting thefirst atomic layer deposition growth rate, wherein the depositing thedielectric layer forms a larger thickness over the spacer than over thesubstrate.
 2. The method of claim 1, wherein the adjusting the firstatomic layer deposition growth rate further comprises introducing F₂. 3.The method of claim 2, wherein the introducing F₂ introduces the F₂ at aflow rate of between about 1 slm and about 3 slm.
 4. The method of claim3, wherein the adjusting the first atomic layer deposition growth rateto a third atomic layer deposition growth rate is performed at atemperature of between about 400° C. and about 500° C.
 5. The method ofclaim 4, wherein the adjusting the first atomic layer deposition growthrate to a third atomic layer deposition growth rate is performed at apressure of about 0 torr.
 6. The method of claim 1, wherein theadjusting the first atomic layer deposition growth rate furthercomprises introducing SF₆.
 7. The method of claim 1, wherein the thirdatomic layer deposition growth rate is smaller than the first atomiclayer deposition growth rate.
 8. A method of manufacturing asemiconductor device, the method comprising: forming a spacer over asubstrate, the spacer comprising first terminal groups and the substratecomprising second terminal groups different from the first terminalgroups; modifying the second terminal groups, wherein after themodifying the second terminal groups the first terminal groups remain;and growing a dielectric layer over both the substrate and the spacerafter the modifying the second terminal groups, wherein after thegrowing the dielectric layer the dielectric layer has a smallerthickness adjacent to the substrate than adjacent to the spacer.
 9. Themethod of claim 8, wherein the modifying the second terminal groupscomprises introducing F₂.
 10. The method of claim 8, wherein themodifying the second terminal groups comprises introducing SF₆.
 11. Themethod of claim 10, wherein the introducing SF₆ is performed at a flowrate of between about 1 slm and about 3 slm.
 12. The method of claim 8,wherein after the growing the dielectric layer the dielectric layer hasa thickness of less than 10 Å adjacent to the substrate.
 13. The methodof claim 12, wherein after the growing the dielectric layer thedielectric layer has a thickness of between about 48 Å and about 52 Åadjacent to the spacer.
 14. The method of claim 8, wherein the growingthe dielectric layer is performed at least in part with an atomic layerdeposition process.
 15. A method of manufacturing a semiconductordevice, the method comprising: forming a spacer adjacent to a gate stackover a semiconductor substrate, the spacer having first terminal groupswith a first bond dissociation energy, the semiconductor substratehaving second terminal groups with a second bond dissociation energyless than the first bond dissociation energy; changing the secondterminal groups to third terminal groups, the third terminal groupshaving a third bond dissociation energy greater than the first bonddissociation energy; and reacting a first precursor with both the firstterminal groups and the third terminal groups to deposit a dielectriclayer.
 16. The method of claim 15, wherein the second bond dissociationenergy is 298 kJ/mol.
 17. The method of claim 16, wherein the first bonddissociation energy is 439 kJ/mol.
 18. The method of claim 17, whereinthe third bond dissociation energy is 565 kJ/mol.
 19. The method ofclaim 15, wherein the dielectric layer has a first thickness adjacent tothe semiconductor substrate that is smaller than a second thicknessadjacent to the spacer.
 20. The method of claim 15, wherein the changingthe second terminal groups to the third terminal groups comprisesreplacing hydrogen atoms with fluorine atoms.